CN1831055B - Ink for ink-jet recording - Google Patents

Ink for ink-jet recording Download PDF

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Publication number
CN1831055B
CN1831055B CN2006100595991A CN200610059599A CN1831055B CN 1831055 B CN1831055 B CN 1831055B CN 2006100595991 A CN2006100595991 A CN 2006100595991A CN 200610059599 A CN200610059599 A CN 200610059599A CN 1831055 B CN1831055 B CN 1831055B
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China
Prior art keywords
ink
printing ink
pigment
glycol
glycol ether
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CN2006100595991A
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CN1831055A (en
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野口亜希子
川口隆
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Brother Industries Ltd
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Brother Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/613—Polyethers without nitrogen
    • D06P1/6138—Polymerisation products of glycols, e.g. Carbowax, Pluronics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65131—Compounds containing ether or acetal groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/30—Ink jet printing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
    • Y10T428/249995—Constituent is in liquid form
    • Y10T428/249996—Ink in pores
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
    • Y10T442/184—Nonwoven scrim
    • Y10T442/198—Coated or impregnated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer

Abstract

A pigment ink for ink-jet recording which is excellent in freezing resistance and fixability includes a pigment, an aqueous resin emulsion, polyethylene glycol and diethylene glycol. This ink satisfies the following formulae (1), (2) and (3) : A<15... (1); A+B> 10... (2); 30 <= A x alpha + B <= 64... (3), wherein: A is the content of polyethylene glycol (%); B is the content of diethylene glycol(%); and +- is the molecular weight ratio of polyethylene glycol to diethylene glycol.

Description

The printing ink that is used for ink-vapor recording
Technical field
The printing ink that is used for ink-vapor recording of the present invention relates to have fabulous winter hardiness (freezing resistance) and anchorage (fixability).
Background technology
Usually, comprise be dispersed in the aqueous medium, as the printing ink of the water-soluble dye of tinting material by generally as ink for ink-jet recording.Recently, consider weathering resistance and water-repellancy, also used the pigment ink that replaces water-soluble dye with pigment.
In pigment ink, use resin aqueous emulsion to improve the dispersibility and the anchorage of pigment, particularly when using printing ink on fabric, to print, improved its washing fastness (seeing the Japanese Patent Application Publication communique 2003-335986 number) by this method.
Yet the conventional printing ink that is used for ink-vapor recording that comprises resin aqueous emulsion can freeze at-5 ℃ to-10 ℃.Therefore, when printing ink being transported to for example cold district, thereby printing ink can freeze to destroy emulsion.In the case, even printing ink returns to room temperature, required ink property can not recover yet.
For solving frozen problem, a kind of printing ink (seeing that Japanese patent application postpones to disclose 2001-81372 number) that uses specified polyoxyethylene alkyl ether sulfate salt as dispersion agent has been proposed.
Summary of the invention
Therefore, the objective of the invention is provides the printing ink that is used for ink-vapor recording with fabulous winter hardiness and anchorage with low cost, even and if use the ink material of more conventional purpose also can reach above purpose in pigment ink.
The inventor finds, is comprising the printing ink that is used for ink-vapor recording of pigment, resin aqueous emulsion, polyoxyethylene glycol and glycol ether, content that can be by regulating polyoxyethylene glycol and glycol ether, makes it satisfy certain relation, thus the realization above-mentioned purpose.
Therefore, the invention provides a kind of printing ink that is used for ink-vapor recording that comprises pigment, resin aqueous emulsion, polyoxyethylene glycol and glycol ether.The described printing ink that is used for ink-vapor recording satisfies following relational expression (1), (2) and (3):
A＜10 ...(1)
A+B＞10 ...(2)
30≤A×α+B≤64 ...(3)
In the formula: A% is the mass percentage content of polyoxyethylene glycol; B% is the mass percentage content of glycol ether; α is a polyoxyethylene glycol and the ratio of the molecular weight of glycol ether.
Become dry and result in blockage in ink gun for fear of printing ink, simultaneously in order to regulate the viscosity of printing ink, the printing ink that the present invention is used for ink-vapor recording comprises polyoxyethylene glycol and the glycol ether as water-miscible organic solvent.
Polyoxyethylene glycol can greatly improve viscosity.Yet if the too high levels of polyoxyethylene glycol, the anchorage of printing ink can variation.The content of glycol ether is high more, is beneficial to more to prevent that printing ink from becoming dry.Yet, if the too high levels of glycol ether, anchorage can affect adversely (though its influence degree not as polyoxyethylene glycol so big).
In printing ink of the present invention, the content of polyoxyethylene glycol is less than 10 quality %.Thus, under the prerequisite that polyoxyethylene glycol is suppressed at the influence of anchorage in the scope that is allowed, appropriateness has increased the viscosity of printing ink.
In addition, printing ink of the present invention satisfies relational expression (2) and (3), so it has fabulous winter hardiness and anchorage simultaneously.Printing ink particularly of the present invention also has fabulous anchorage on fabric.Therefore, when ink printing was on fabric, prepared print had fabulous washing fastness.
In addition, therefore printing ink of the present invention can low cost make by mixing conventional purpose ink material preparation.
Embodiment
To describe the present invention in detail below.In the following description, unless otherwise indicated, " % " expression quality %.
The printing ink that the present invention is used for ink-vapor recording comprises pigment, resin aqueous emulsion, polyoxyethylene glycol and glycol ether.
In printing ink of the present invention, mineral dye or the pigment dyestuff that is generally used for ink for ink-jet recording can be used as pigment, and not have special restriction.The example of pigment dyestuff comprises: azo pigment, for example azo lake, insoluble azo colour, concentrated azo pigment, chelating azo pigment etc.; Many ring pigment, for example phthalocyanine pigment, perylene pigments, anthraquinone pigment, quinacridone pigment, triazine dioxin pigment, thioindigo color, isoindolinone pigment, quinophthalone (quinophthalone) pigment etc.; The dyestuff color lake, for example alkaline active class (basicreactive type) color lake, matching stain class color lake etc.; Nitropigments; Nitroso pigments; Nigrosine; High-visibility pigment; Deng.The example of mineral dye comprises titanium oxide, ferric oxide, carbon black etc.Specifically, in order to show distinct color, preferably with C.I.Pigment Yellow 3,4,5,7,17,50,51,81,98,105,180 etc. as yellow ultramarine.In addition, preferably with C.I.Pigment Red 2,3,5,16,23,31,49,57,63,122 etc. as magenta pigment, preferably with C.I.Pigment Blue 1,2,15:3,16,17 etc. as green pigment.
If the undersized of pigment, just then printing density, pigment can't be satisfactory to character such as the covering character of base material, dispersing of pigments stability.If granularity is excessive, then stop up ink gun easily, and character such as ink color vividness, colo(u)rant dispersion stability can't be satisfactory.Therefore, the equal granularity of body (averagevolume particle size) preferably is about the 50-200 nanometer.
Consider colour balance, the concentration of yellow ultramarine, magenta pigment and green pigment and so on coloured pigment preferably is about 3-5% in the printing ink.The content of black pigment is high more good more, and this is owing to can be very important in the density of the enterprising line item of recording medium.Yet, if the too high levels of black pigment can reduce from the ability of ink gun ink jet.Therefore, its content preferably is about 6-10%.
Sneak into described resin aqueous emulsion as tackiness agent, pigment is dispersed or mixes.Particularly when on fabric, carrying out ink jet printing, can improve washing fastness by sneaking into resin aqueous emulsion.
The emulsion that various second-order transition temperatures can be approximated or be lower than 0 ℃ resin is used as described resin aqueous emulsion.The object lesson of resin aqueous emulsion comprises acrylic acid or the like base emulsion, urethanum base emulsion, polyester based emulsion, polystyrene base emulsion, their combination etc.Acrylic acid or the like base emulsion preferably wherein.
There is no particular restriction to the character of these resin aqueous emulsions, and anionic emulsion, cation emulsion and nonionic emulsion etc. all can be used.In addition, microemulsion, thick emulsion (gross emulsion), active emulsion, ambient crosslinking emulsion, any kind that has in the emulsions such as emulsion of double-layer structure all can be used.The equal granularity of body that constitutes the resin particle of this emulsion preferably is about the 10-200 nanometer, especially preferably is about the 50-150 nanometer.
If the content of resin aqueous emulsion is low excessively, then dispersibility and anchorage can not be satisfactory.Specifically, when ink printing on fabric the time, is faded in washing process.On the other hand, if too high levels can reduce from the ability of ink gun ink jet.Therefore, in the present invention, the content of described resin aqueous emulsion (with solid content meter) preferably is about 6-10%.
Use polyoxyethylene glycol and glycol ether viscosity modifier,, prevent that printing ink from becoming dry and the obstruction ink gun simultaneously as wetting agent as printing ink.The molecular weight of polyoxyethylene glycol is big more, and nozzle generation ejection failure is frequent more.On the other hand, if molecular weight then can solidify at about 25 ℃ up to about 600.In the case, the adhesive capacity of this kind printing ink on printing material is better than at 25 ℃ and is the printing ink of liquid down, thereby obtains good anchorage.Therefore, the molecular weight of polyoxyethylene glycol preferably is about 200-600.
Feature of the present invention is that the content of polyoxyethylene glycol and glycol ether satisfies following relational expression (1), (2) and (3):
A＜10 ...(1)
A+B＞10 ...(2)
30≤A×α+B≤64 ...(3)
In the formula: A is the mass percentage content of polyoxyethylene glycol; B is the mass percentage content of glycol ether; α is a polyoxyethylene glycol and the ratio of the molecular weight of glycol ether.
Be adjusted to approximately less than 10% (formula (1)) by content, preferably be approximately equal to or less than 10%, can on the basis of the anchorage variation that does not make printing ink, effectively increase its viscosity polyoxyethylene glycol.
By in the scope that satisfies formula (3) total content of polyoxyethylene glycol and glycol ether being adjusted to approximately greater than 10% (formula (2)), printing ink can have fabulous winter hardiness and fabulous anchorage simultaneously.If the total content of polyoxyethylene glycol and glycol ether is approximately equal to or less than 10%, then winter hardiness is abundant inadequately.
The reason that improves winter hardiness and anchorage by satisfying formula (3) simultaneously it be unclear that.Can think that it is relevant to cause depression of the freezing point phenomenon to improve therewith owing to molecule number in the solvent increases.Formula (3) is the inventor's new discovery with the relation of winter hardiness and anchorage.
In the present invention, preferably in the scope that satisfies relational expression (1), (2) and (3), suitably determine the content of polyoxyethylene glycol and glycol ether according to the factors such as kind of pigment and emulsion.For example, the solids content in the black ink is usually greater than colored ink, even therefore do not add polyoxyethylene glycol or glycol ether in black ink, black ink also has high viscosity.Therefore, compare with the content of polyoxyethylene glycol in the colored ink and glycol ether, the content of these materials can reduce in the black ink.
Except said components, printing ink of the present invention preferably comprises as the pure water of aqueous medium or ion exchanged water.Printing ink of the present invention can comprise the water-miscible organic solvent except that polyoxyethylene glycol and glycol ether equally as required.Preferably the boiling point of this water-miscible organic solvent is lower than the boiling point of glycol ether.The example of described water-miscible organic solvent comprises: dibasic alcohol, for example ethylene glycol, propylene glycol, 1,3-ethohexadiol, dipropylene glycol, 1,3 propylene glycol, hexylene glycol etc.; Glycol, for example glycol monomethyl first, ethylene glycol diethyl, ethylene glycol only son, ethylene glycol bisthioglycolate fourth, glycol monomethyl are different third, oneself, glycerine diformazan, glycerine diethyl, glycol ether ethyl-methyl, glycol ether diethyl, glycol ether diformazan, diglycol monotertiary first, glycol ether only son, diglycol monotertiary second, triglycol diformazan, triglycol list first, propylene glycol list second, propylene glycol only son, propylene glycol list of glycol monomethyl is first-class; Pure and mild polyvalent alcohol, for example ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,4-butylene glycol etc.; And ester, for example ethylene glycol bisthioglycolate ethyl ester, glycol monomethyl ethyl ester, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate etc.The mixed use of above-mentioned water-miscible organic solvent.
Be used for the printing ink of ink-vapor recording, the content of these water-miscible organic solvents preferably is about 5-50%.The printing ink that is particularly preferred for ink-vapor recording satisfies following relational expression (4):
30≤A×α+(B+C)≤64 ...(4)
In the formula: A is the mass percentage content of polyoxyethylene glycol; B is the mass percentage content of glycol ether; C be except that polyoxyethylene glycol and glycol ether, boiling point is lower than the mass percentage content of the water-miscible organic solvent of glycol ether; α is a polyoxyethylene glycol and the ratio of the molecular weight of glycol ether.
In printing ink of the present invention, except boiling point is lower than the water-miscible organic solvent of glycol ether, also can use boiling point to be higher than the water-soluble solvent of glycol ether, need only it and can not cause negative impact anchorage.The example that this boiling point is higher than the water-miscible organic solvent of glycol ether comprises: glycol ethers, for example glycerine, triglycol, 3 third glycol, diethylene glycol dibutyl ether, triglycol list ether, triethylene glycol monomethyl ether etc.; And ester, for example glycerine 1,3-diacetate esters, triacetin, diglycol monotertiary acetic ester, diethylene glycol monobutyl ether acetic ester etc.
In addition, printing ink of the present invention can comprise following additive as required: viscosity modifier, for example polyvinyl alcohol, Mierocrystalline cellulose etc.; Dispersion agent, for example water-soluble polymers etc.; Tensio-active agent; The pH regulator agent; Antifoams; Preservatives; Deng.
Preferably use above-mentioned polyoxyethylene glycol and glycol ether, the viscosity modifier that use simultaneously adds as required arrives about 3-20cP, especially preferably about 12-14cP with the viscosity adjustment of printing ink of the present invention.
The method for preparing printing ink of the present invention preferably includes: the first step, with colo(u)rant dispersion in aqueous medium; In second step, in the dispersion that the first step makes, add water-based emulsion, polyoxyethylene glycol and glycol ether.
In the first step, by pulverizer or dispersion machine with colo(u)rant dispersion in aqueous medium, if necessary, remove coarse particles by methods such as centrifugal, filtrations, thereby make the dispersing of pigments body.The example of pulverizer and dispersion machine comprises ball mill, ball mill, sand mill, attritor, roller mill, mixer grinder, Henschel mixer, colloidal mill, ultrasonic homogenizer, pearl shredder, jet mill, Ang shredder and Mechanofusion (production of Hosokawa Micron company limited).
In second step, resin aqueous emulsion, polyoxyethylene glycol and glycol ether are added in the pigment dispersion that the first step makes.Mixture to gained stirs, and makes the component homodisperse, if desired, this mixture is filtered, thereby obtains printing ink.
Preferably, add additive as required in second step.
The printing ink that is used for ink-vapor recording that makes like this is used in the piezoelectric ink jet printing press that print head has piezoelectric element.Preferably, when using ink-jet printer on recording medium, to print target compound, by the printing target compound is carried out heat treated---for example use hot-rolling, thermocompressor, flatiron etc. to heat-treat; Heat-treat by the warm air air blowing; Steam heat processing etc.---will print target compound and be fixed on the recording medium.
When with ink jet on fabric the time, the amount of droplets of ink preferably is about 0-50pL/ and drips.In addition, preferably use thermocompressor, be about 130-180 ℃ in temperature, pressure approximates or handles about 15-120 second down greater than the heating and the pressurized conditions of 0.01 MPa, thereby fixes.
The example that can use printing ink of the present invention to carry out the recording medium of ink jet printing thereon comprises: the scraps of paper, for example plain paper, special-purpose paper etc.; Fabric, for example woven fabric, knitted fabrics, non-woven fabric etc.; Timber; Corrugated cardboard; Deng.Specifically, in order to be suitable for heat setting, the fabric of woven fabric, knitted fabrics, non-woven etc. and so on preferably.The fiber that constitutes fabric is not particularly limited.The example of these fibers comprises: natural fiber, for example cotton, silk, hemp, wool etc.; Synthon, for example polymeric amide, polyester, acrylic acid or the like etc.; Regenerated fibre and semi-synthetic fibre, for example artificial silk, acetic ester etc.; The blend fiber of these fibers; Deng.In addition, consider that the example of preferred recording medium comprises the white T-shirt textiles of 100% textile system from factors such as skin feel, water-absorbent, cost, availabilities.
Embodiment
Describe the present invention in detail with reference to following embodiment below.
(1) preparation of printing ink
Prepared following printing ink: have the Yellow ink of forming shown in the table 1; Has the magenta ink of forming shown in the table 2; Has the cyan ink of forming shown in the table 3; Has the black ink of forming shown in table 4A, 4B and the 4C.
In these printing ink, C.I.Pigment Yellow 74 as yellow ultramarine, is used as magenta ink with C.I.Pigment Red122.C.I.Pigment Blue 15:3 as green pigment, is used as black ink with C.I.PigmentBlack 7.
In various coloured pigments, use identical pigment concentration (4%) and identical resin aqueous emulsion concentration (solids content: 8%).Composition to shades of colour printing ink is regulated, make that for following every kind of polyethyleneglycol content be in 0%, 5%, 10% and 15% the printing ink, the total content of polyoxyethylene glycol (PEG, molecular weight=400) and glycol ether (DEG) is 10%, 20%, 30%, 40%, 50% and 60%.
In black ink, pigment concentration is 8%, and is identical with the situation of colored ink, and using molecular weight is the black ink that 400 PEG preparation has various compositions.In addition, prepared other two groups of black inks similarly, in these two groups, using molecular weight is that 200 or 600 PEG substituted molecule amount is 400 PEG.
During preparation printing ink, at first use dispersion machine (Sand Grinder, Igarashi Kikai produces) pigment (20%), glycol ether (10%) and ion exchanged water (70%) are stirred more than 30 minutes or 30 minutes, each component is disperseed, thereby make pigment dispersion.In the pigment dispersion that makes, add resin aqueous emulsion (acrylic resin, ProductName: Joncryl 1674 (solids content: 45%), the production of Johnson Polymer company limited), polyoxyethylene glycol (PEG, 200,400 or 600) and glycol ether (DEG, molecular weight: 106) molecular weight:.This mixture stirred 5 minutes, used 3 microns membrane filter or 5 microns metallic filter to filter the dispersion that makes under pressure.
(2) assessment
(2-1) winter hardiness
Printing ink in each test implementation example (10 milliliters) is placed in the container, in-15 ℃ thermostatic bath, left standstill 30 minutes.According to following criterion evaluation winter hardiness.
A; Printing ink does not freeze.
B: printing ink freezes.
(2-2) anchorage
The drop amount of using ink-jet printer to drip with 600dpi * 600dpi, 40pL/ is made the ink printing in each test implementation example on the T-shirt at 100% cotton textiles.Use thermocompressor, under 130 ℃ design temperature to the T-shirt thermal treatment of printing 30 seconds.
II type (Gakushin type) friction testing machine (wearability test machine, ImotoMachinery company limited produces) by JIS 0849 regulation uses the printing T-shirt friction reciprocation cycle (Reciprocal cycle) of general T shirt fabric (test specimen) to making.Measure the colorant density on the test specimen then, anchorage is carried out classification by following standard.
A: less than 0.03
B: more than or equal to 0.03, less than 0.04
C: more than or equal to 0.04
Gained the results are shown in following table 1-5D.
Table 1
Yellow ink
(yellow ultramarine: 4%, resin aqueous emulsion (solids content): 8%)
(unit: %)
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
1 0 10 10 C A
2 0 20 20 C A
3 0 30 30 B A
4 0 40 40 B A
5 0 50 50 B A
6 0 60 60 B A
7 5 5 10 C A
8 5 15 20 B A
9 5 25 30 B A
10 5 35 40 B A
11 5 45 50 B B
12 5 55 60 B C
13 10 0 10 ( *1)
14 10 10 20 B A
15 10 20 30 B A
16 10 30 40 B A
17 10 40 50 B C
18 10 50 60 B C
19 15 10 ( *2)
20 15 5 20 B C
21 15 15 30 B C
22 15 25 40 B C
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
23 15 35 50 B C
24 15 45 60 B C
( *1) because pigment dispersion comprises DEG, can't prepare the printing ink that comprises predetermined amount DEG.
( *2) when the content of PEG is 15%, can't prepare the printing ink that comprises 10% " PEG+DEG ".
Table 2
Magenta ink
(magenta pigment: 4%, resin aqueous emulsion (solids content): 8%)
(unit: %)
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
1 0 10 10 C A
2 0 20 20 C A
3 0 30 30 B A
4 0 40 40 B A
5 0 50 50 B A
6 0 60 60 B A
7 5 5 10 C A
8 5 15 20 B A
9 5 25 30 B A
10 5 35 40 B A
11 5 45 50 B B
12 5 55 60 B C
13 10 0 10 ( *1)
14 10 10 20 B A
15 10 20 30 B A
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
16 10 30 40 B A
17 10 40 50 B C
18 10 50 60 B C
19 15 -5 10 ( *2)
20 15 5 20 B C
21 15 15 30 B C
22 15 25 40 B C
23 15 35 50 B C
24 15 45 60 B C
( *1) because pigment dispersion comprises DEG, can't prepare the printing ink that comprises predetermined amount DEG.
( *2) when the content of PEG is 15%, can't prepare the printing ink that comprises 10% " PEG+DEG ".
Table 3
Cyan ink
(green pigment: 4%, resin aqueous emulsion (solids content): 8%)
(unit: %)
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
1 0 10 10 C A
2 0 20 20 C A
3 0 30 30 B A
4 0 40 40 B A
5 0 50 50 B A
6 0 60 60 B A
7 5 5 10 C A
8 5 15 20 B A
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
9 5 25 30 B A
10 5 35 40 B A
11 5 45 50 B B
12 5 55 60 B C
13 10 0 10 ( *1)
14 10 10 20 B A
15 10 20 30 B A
16 10 30 40 B C
17 10 40 50 B C
18 10 50 60 B C
19 15 -5 10 ( *2)
20 15 5 20 B C
21 15 15 30 B C
22 15 25 40 B C
23 15 35 50 B C
24 15 45 60 B C
( *1) because pigment dispersion comprises DEG, can't prepare the printing ink that comprises predetermined amount DEG.
( *2) when the content of PEG is 15%, can't prepare the printing ink that comprises 10% " PEG+DEG ".
Table 4A
Black ink
(black pigment: 8%, resin aqueous emulsion (solids content): 9.5%, PEG molecular weight: 200)
(unit: %)
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
1 0 10 10 C A
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
2 0 20 20 C A
3 0 30 30 B A
4 0 40 40 B A
5 0 50 50 ( *1)
6 0 60 60 ( *1)
7 5 5 10 C A
8 5 15 20 B A
9 5 25 30 B A
10 5 35 40 B B
11 5 45 50 ( *1)
12 5 55 60 ( *1)
13 10 0 10 ( *2)
14 10 10 20 B A
15 10 20 30 B A
16 10 30 40 B A
17 10 40 50 ( *1)
18 10 50 60 ( *1)
19 15 -5 10 ( *2)
20 15 5 20 B A
21 15 15 30 B B
22 15 25 40 B B
23 15 35 50 ( *1)
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
24 15 45 60 ( *1)
( *1) must be with 40% pigment dispersion (pigment solids content: 20%) with 21% resin aqueous emulsion (solids content: 45%) mix, thereby preparation comprises the printing ink of 8% pigment and 9.5% resin aqueous emulsion (solids content).Therefore, the maximum level of PEG+DEG is 39%, and " PEG+DEG " content can't be adjusted to preset value.
( *2) because pigment dispersion comprises DEG, can't prepare the printing ink that comprises predetermined amount DEG.
Table 4B
Black ink
(black pigment: 8%, resin aqueous emulsion (solids content): 9.5%, PEG molecular weight: 400)
(unit: %)
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
1 0 10 10 C A
2 0 20 20 C A
3 0 30 30 B A
4 0 40 40 B A
5 0 50 50 ( *1)
6 0 60 60 ( *1)
7 5 5 10 C A
8 5 15 20 B A
9 5 25 30 B A
10 5 35 40 B A
11 5 45 50 ( *1)
12 5 55 60 ( *1)
13 10 0 10 ( *2)
14 10 10 20 B A
15 10 20 30 B A
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
16 10 30 40 B B
17 10 40 50 ( *1)
18 10 50 60 ( *1)
19 15 -5 10 ( *2)
20 15 5 20 B C
21 15 15 30 B C
22 15 25 40 B C
23 15 35 50 ( *1)
24 15 45 60 ( *1)
( *1) must be with 40% pigment dispersion (pigment solids content: 20%) with 21% resin aqueous emulsion (solids content: 45%) mix, thereby preparation comprises the printing ink of 8% pigment and 9.5% resin aqueous emulsion (solids content).Therefore, the maximum level of PEG+DEG is 39%, and " PEG+DEG " content can't be adjusted to preset value.
( *2) because pigment dispersion comprises DEG, can't prepare the printing ink that comprises predetermined amount DEG.
Table 4C
Black ink
(black pigment: 8%, resin aqueous emulsion (solids content): 9.5%, PEG molecular weight: 600)
(unit: %)
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
1 0 10 10 C A
2 0 20 20 C A
3 0 30 30 B A
4 0 40 40 B A
5 0 50 50 ( *1)
6 0 60 60 ( *1)
7 5 5 10 C A
The test implementation example PEG DEG PEG+DEG Winter hardiness Anchorage
8 5 15 20 B A
9 5 25 30 B A
10 5 35 40 B A
11 5 45 50 ( *1)
12 5 55 60 ( *1)
13 10 0 10 ( *2)
14 10 10 20 B A
15 10 20 30 B A
16 10 30 40 B A
17 10 40 50 ( *1)
18 10 50 60 ( *1)
19 15 -5 10 ( *2)
20 15 5 20 B A
21 15 15 30 B B
22 15 25 40 B C
23 15 35 50 ( *1)
24 15 45 60 ( *1)
( *1) must be with 40% pigment dispersion (pigment solids content: 20%) with 21% resin aqueous emulsion (solids content: 45%) mix, thereby preparation comprises the printing ink of 8% pigment and 9.5% resin aqueous emulsion (solids content).Therefore, the maximum level of PEG+DEG is 39%, and " PEG+DEG " content can't be adjusted to preset value.
( *2) because pigment dispersion comprises DEG, can't prepare the printing ink that comprises predetermined amount DEG.
To the result shown in the table 4, list in table 5A to 5D according to above-mentioned relation formula (3) conclusive table 1.
30≤A×α+B≤64 ...(3)
In the formula: A is the mass percentage content of PEG; B is the mass percentage content of DEG; α=1.9 (200 (molecular weight of PEG)/106 (molecular weight of DEG)), α=3.8 (400 (molecular weight of PEG)/106 (molecular weight of DEG)) or α=5.7 (600 (molecular weight of PEG)/106 (molecular weight of DEG)).
Table 5A
Table 5B
Table 5C
Figure G2006100595991D00151
Table 5D
Figure G2006100595991D00152
From table 1 to table 4C as can be seen, the variation of anchorage depends on the content of polyoxyethylene glycol.Same, even the content of polyoxyethylene glycol is very low, when the too high levels of glycol ether, anchorage also can variation (seeing test implementation example 12).In addition, the content of polyoxyethylene glycol and glycol ether is high more, and winter hardiness is good more.
From table 5A to 5D as can be seen, in the scope that satisfies relational expression (3) (table 5A is to the shadow region of showing among the 5D), when satisfying relational expression (2), winter hardiness and anchorage are all fine.
Printing ink of the present invention can be used as the printing ink that carries out ink-vapor recording on the various recording mediums of fabric comprising.
Whole specification sheets, claims and summary that the Japanese patent application of submitting on March 9th, 2005 is 2005-66405 number all are incorporated by reference into this paper.

Claims (14)

1. method that is used on fabric, carrying out ink-vapor recording, this method comprises:
(a) with ink jet on fabric, this printing ink comprises pigment, resin aqueous emulsion, polyoxyethylene glycol and glycol ether, wherein
Satisfy following relational expression (1), (2) and (3):
A＜10 ...(1)
A+B＞10 ...(2)
30≤A×α+B≤64 ...(3)
In the formula: A% is the mass percentage content of polyoxyethylene glycol; B% is the mass percentage content of glycol ether; α is a polyoxyethylene glycol and the ratio of the molecular weight of glycol ether;
(b) by heat treated printing ink is fixed on the fabric.
2. the method for claim 1 is characterized in that, the molecular weight of polyoxyethylene glycol is 200-600.
3. method as claimed in claim 1 or 2 is characterized in that this printing ink also comprises the water-miscible organic solvent except that polyoxyethylene glycol and glycol ether, and the boiling point of this organic solvent is lower than the boiling point of glycol ether.
4. method as claimed in claim 3 is characterized in that, the described printing ink that is used for ink-vapor recording satisfies following relational expression (4)
30≤A×α+(B+C)≤64 ...(4)
In the formula: C% is the mass percentage content of described water-miscible organic solvent.
5. method as claimed in claim 1 or 2 is characterized in that, this printing ink comprises the black pigment that mass percent is 6-10%.
6. method as claimed in claim 1 or 2 is characterized in that, this printing ink comprises yellow ultramarine, magenta pigment or the green pigment that mass percent is 3-5%.
7. method as claimed in claim 1 or 2 is characterized in that described resin aqueous emulsion comprises the emulsion that contains resin, and the vitrifying point of this resin is equal to or less than 0 ℃.
8. printing ink that is used for ink-vapor recording, this printing ink comprises pigment, resin aqueous emulsion, polyoxyethylene glycol and glycol ether, wherein
Satisfy following relational expression (1), (2) and (3):
A＜10 ...(1)
A+B＞10 ...(2)
30≤A×α+B≤64 ...(3)
In the formula: A% is the mass percentage content of polyoxyethylene glycol; B% is the mass percentage content of glycol ether; α is a polyoxyethylene glycol and the ratio of the molecular weight of glycol ether.
9. the printing ink that is used for ink-vapor recording as claimed in claim 8 is characterized in that, the molecular weight of polyoxyethylene glycol is 200-600.
10. be used for the printing ink of ink-vapor recording as claimed in claim 8 or 9, it is characterized in that, this printing ink also comprises the water-miscible organic solvent except that polyoxyethylene glycol and glycol ether, and the boiling point of this organic solvent is lower than the boiling point of glycol ether.
11. the printing ink that is used for ink-vapor recording as claimed in claim 10 is characterized in that, the described printing ink that is used for ink-vapor recording satisfies following relational expression (4)
30≤A×α+(B+C)≤64 ...(4)
In the formula: C% is the mass percentage content of described water-miscible organic solvent.
12. be used for the printing ink of ink-vapor recording as claimed in claim 8 or 9, it is characterized in that this printing ink comprises the black pigment that mass percent is 6-10%.
13. be used for the printing ink of ink-vapor recording as claimed in claim 8 or 9, it is characterized in that this printing ink comprises yellow ultramarine, magenta pigment or the green pigment that mass percent is 3-5%.
14. be used for the printing ink of ink-vapor recording as claimed in claim 8 or 9, it is characterized in that described resin aqueous emulsion comprises the emulsion that contains resin, the vitrifying point of this resin is equal to or less than 0 ℃.
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